Solvent Effects in Anionic Polymerization. The Behavior of Living Polystyrene in Tetrahydrofuran-Dioxane Mixtures

Beylen, Marcel Van; Bhattacharyya, D.; Smid, J.; Szwarc, M.

doi:10.1021/j100873a024

Cited by 28 publications

(7 citation statements)

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“…Other solvent effects are also known to impact polymerization reactions. For example, the propagation rate is strongly correlated to the stability of the solvent-separated ion pair that is formed during anionic polymerization. − Similar effects have been observed in cationic polymerizations and free radical polymerizations − and are reviewed elsewhere . In controlled radical polymerizations, where the concentration of reactive chain ends is very low, complexation of the chain end with the solvent is less important in determining the rate of polymerization.…”

Section: The Role Of Solvents In Covalent Chemistrymentioning

confidence: 86%

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

2020

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Interactions between solvents and solutes are a cornerstone of physical organic chemistry and have been the subject of investigations over the last century. In recent years, a renewed interest in fundamental aspects of solute–solvent interactions has been sparked in the field of supramolecular chemistry in general and that of supramolecular polymers in particular. Although solvent effects in supramolecular chemistry have been recognized for a long time, the unique opportunities that supramolecular polymers offer to gain insight into solute–solvent interactions have become clear relatively recently. The multiple interactions that hold the supramolecular polymeric structure together are similar in strength to those between solute and solvent. The cooperativity found in ordered supramolecular polymers leads to the possibility of amplifying these solute–solvent effects and will shed light on extremely subtle solvation phenomena. As a result, many exciting effects of solute–solvent interactions in modern physical organic chemistry can be studied using supramolecular polymers. Our aim is to put the recent progress into a historical context and provide avenues toward a more comprehensive understanding of solvents in multicomponent supramolecular systems.

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Section: The Role Of Solvents In Covalent Chemistrymentioning

confidence: 86%

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

2020

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“…The solvent polarity and the solvation of the living chain ends have a tremendous influence on the propagation rate in ionic polymerizations. 2,3,24 For the azaanionic ROP of MsMAz (1) at 50°C, polar solvents such as DMSO-d 6 (k p = 13.17 ± 0.7 × 10 −3 L mol −1 s −1 (mean value from repeated measurements I (Fig. 2 and Table 2).…”

Section: Solvent Variationmentioning

confidence: 99%

The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics

et al. 2017

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“…It is further known that apolar solvents slow down the reaction rate of anionic polymerisations [60] . Within the experimental work, the initiator butyllithium was solved in hexane, whereas the monomer styrene was solved in THF.…”

Section: Experimental Polymerisationmentioning

confidence: 99%

Evaluation of different micromixers by CFD simulations for the anionic polymerisation of styrene

Ziegenbalg

Kompter

Schönfeld³

et al. 2012

Green Processing and Synthesis

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To ensure a suffi cient reaction control, including fast mixing and heat removal, microstructured devices were chosen to conduct anionic polymerisations. To decrease the experimental effort and the resulting costs, a numerical approach was followed to apply decision support during experimental planning. Semi-quantitative CFD calculations were used to determine the best suited micromixer out of a collection of different devices. Using the numerical investigated micromixers for experimental investigations, the general order gained from CFD calculations was confi rmed. It could be shown that CFD calculations can benefi cially be used to rank micromixing devices for specifi c process conditions and synthesis tasks. List of abbreviationsA area (m 2 ) CFD computational fl uid dynamics c concentration (mol/m 3 ) D binary diffusion coeffi cient (m 2 /s) d h hydraulic diameter k p rate constant of propagation (l/mol/s) ṁ mass fl ow rate (g/s) M molar mass (g/mol) p pressure (N/m 2 ) r mixing residuum (1) s length (m) t time (s) t R space time (s) t M ,95 % mixing time to achieve 95 % mixing quality v velocity vector (m/s) V volume fl ow rate (ml/min) w mass fraction (1) Indices D diffusion i; n control variable Init initiator max maximum perf perfect Mono monomer rel relative seg segregated sum sum/summed Greek symbols η viscosty (Pa × s) ρ density (kg/m 3 ) Δ R H reaction enthalpy (kJ/mol)

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Solvent Effects in Anionic Polymerization. The Behavior of Living Polystyrene in Tetrahydrofuran-Dioxane Mixtures

Cited by 28 publications

References 1 publication

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics

Evaluation of different micromixers by CFD simulations for the anionic polymerisation of styrene

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